A. Aravind, P. S. Kumar, M. G. Sankar, S. Baskaran
FULL PAPER
= 11.2, 6.4 Hz, 1 H), 3.94 (dd, J = 11.2, 2.5 Hz, 1 H), 3.96–4.02
1
1372, 1255, 1215, 1064, 858 cm–1. H NMR (400 MHz, CDCl3): δ
(m, 2 H), 4.07–4.17 (m, 1 H), 4.23 (AB quartet, J = 11.7 Hz, 2 H), = 1.38 (s, 3 H), 1.42 (s, 3 H), 3.16 (s, 3 H), 3.67–3.75 (m, 2 H),
4.54 (AB quartet, J = 11.7 Hz, 2 H), 4.76–4.80 (m, 1 H), 7.09–7.13
(m, 2 H), 7.27–7.36 (m, 14 H), 7.65–7.68 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 19.3, 26.9, 38.4, 69.0, 69.6, 70.3, 71.3, 72.6,
73.1, 73.5, 80.5, 127.5, 127.6, 127.7, 127.7, 127.8, 128.3, 128.4,
129.7, 129.9, 132.4, 133.6, 135.7, 136.0, 137.4, 137.5 ppm. HRMS
(ESI): calcd. for C37H46O8SSiNa [M + Na]+ 701.2580; found
701.2593.
3.83–3.86 (m, 1 H), 3.92 (dd, J = 5.2 Hz, 1 H), 3.98 (dd, J = 4.0 Hz,
1 H), 4.37 (dd, J = 3.6, 6.8 Hz, 1 H), 4.89 (dd, J = 4.4, 8.8 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.9, 26.9, 38.5, 61.4,
63.9, 73.6, 76.6, 79.1, 81.9, 110.2 ppm. HRMS (ESI): calcd. for
C10H20O8SNa [M + Na]+ 323.0777; found 323.0786.
(3aS,7R,7aS)-4-Hydroxy-2,2-dimethyl-tetrahydro-3aH-[1,3]dioxolo-
[4,5-c]pyran-7-yl Methanesulfonate (7):[20d] To a stirred solution of
compound 6 (300 mg, 1 mmol) in DCM (20 mL) was added NaIO4/
SiO2 (2 g, 2.3 mmol based on NaIO4), and the resultant mixture
was stirred at room temperature for 3 h. The reaction was filtered
and the residue was washed with DCM (2ϫ10 mL), and the com-
bined organic layers were concentrated under reduced pressure to
yield the crude compound. Chromatographic purification of the
crude compound using silica gel (gradient elution with 80–100%
EtOAc in hexane) yielded pure compound 7 (255 mg, 95%) as a
(R)-2-(Benzyloxy)-1-{(4S,5S)-5-[(R)-2-(benzyloxy)-1-(tert-butyldi-
phenylsilyloxy)ethyl]-2,2-dimethyl-1,3-dioxolan-4-yl}ethyl Methane-
sulfonate (4): To a stirred solution of compound 1a (800 mg,
1.18 mmol) in dry acetone (15 mL) was added DMP (306 mg,
2.94 mmol) and a catalytic amount of CSA (camphorsulfonic acid).
The resultant mixture was stirred at room temperature for 4 h. The
reaction mixture was concentrated under reduced pressure. Purifi-
cation by column chromatography over silica gel (gradient elution
with 10–20% EtOAc in hexane) gave pure compound 4 (678 mg,
80%) as a viscous liquid. [α]2D6 = +4.0 (c = 1.0, CHCl3). IR (neat):
colorless viscous liquid. [α]2D0 = –1.2 (c = 0.4, CHCl ). IR (neat): ν
˜
3
= 3421, 3052, 2926, 2854, 1732, 1455, 1362, 1264, 1174, 1108 cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.38 (s, 1 H), 1.44 (s, 6 H), 1.52
(s, 1 H), 3.15 (s, 0.9 H), 3.15 (s, 3 H), 3.54–3.62 (m, 0.6 H), 3.82–
3.94 (m, 1.7 H), 3.95–4.07 (m, 1.6 H), 4.09–4.21 (m, 1.6 H), 4.33–
4.38 (m, 0.6 H), 4.52 (dd, J = 0.8, 6.4 Hz, 0.3 H), (dd, J = 2.4,
9.6 Hz, 1 H), 4.85–4.86 (m, 1 H), 9.80 (d, J = 0.84 Hz, 0.2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 14.1, 15.0, 18.2, 25.7, 26.4, 26.7,
27.0, 38.5, 38.6, 38.6, 38.5, 58.2, 60.3, 61.9, 63.4, 63.9, 75.1, 76.3,
79.8, 80.6, 81.1, 81.6, 81.8, 95.5, 110.2, 110.7, 111.7, 201.2 ppm.
HRMS (ESI): calcd. for C9H16O7SNa [M + Na]+ 291.0514; found
291.0504.
ν = 3424, 2928, 2664, 1360, 1177, 1107, 697 cm–1 1H NMR
.
˜
(400 MHz, CDCl3): δ = 1.05 (s, 9 H), 1.33 (s, 3 H), 1.35 (s, 3 H),
2.93 (s, 3 H), 3.36 (dd, J = 10.0, 4.8 Hz, 1 H), 3.49 (dd, J = 10.0,
5.3 Hz, 1 H), 3.64 (d, J = 5.2 Hz, 2 H), 4.07 (dd, J = 9.3, 4.7 Hz,
1 H), 4.19 (AB quartet, J = 11.7 Hz, 2 H), 4.28 (dd, J = 6.5, 4.1 Hz,
1 H), 4.40–4.50 (m, 3 H), 4.89 (dd, J = 10.3, 5.2 Hz, 1 H), 7.10 (m,
2 H), 7.21–7.39 (m, 14 H), 7.69–7.72 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 19.4, 27.0, 27.3, 27.4, 38.7, 68.8, 70.7, 71.7,
72.9, 73.3, 75.9, 79.0, 80.6, 109.9, 127.4, 127.5, 127.6, 127.7, 127.8,
128.1, 128.4, 128.5, 129.6, 129.7, 133.1, 134.1, 135.8, 136.1, 137.4,
138.0 ppm. HRMS (ESI): calcd. for C40H50O8SSiNa [M + Na]+
741.2893; found 741.2870.
(R)-1-{(4S,5S)-5-[(R)-1-(tert-Butyldiphenylsilyloxy)-2-hydroxyeth-
yl]-2,2-dimethyl-1,3-dioxolan-4-yl}-2-hydroxyethyl Methanesulfon-
ate (8): To a stirred solution of compound 4 (800 mg, 1.11 mmol)
in EtOH (20 mL) was added Pd/C (10 wt.-%, 80 mg). The mixture
was stirred under a hydrogen atmosphere (60 psi using a Parr hy-
drogenator) for 3 d. The reaction mixture was filtered, and the fil-
trate was concentrated under reduced pressure. The crude com-
pound was purified by column chromatography over silica gel (gra-
dient elution with 40–60% EtOAc in hexane) to afford pure diol 8
(R)-2-(Benzyloxy)-1-{(4S,5R)-5-[(R)-2-(benzyloxy)-1-hydroxyethyl]-
2,2-dimethyl-1,3-dioxolan-4-yl}ethyl Methanesulfonate (5): To a
stirred solution of compound 4 (1 g, 1.39 mmol) in dry THF
(10 mL) was added TBAF (1 m solution in THF, 6 mL, 5.5 mmol),
and the resultant mixture was stirred at room temperature for 6 h.
The reaction mixture was concentrated and then diluted with
EtOAc (30 mL). The organic layer was washed with water
(2ϫ10 mL), dried with anhydrous Na2SO4, and concentrated un-
der reduced pressure. Chromatographic purification of the crude
compound over silica gel (gradient elution with 30–40% EtOAc in
hexane) yielded pure compound 5 (500 mg, 75%) as a colorless
(570 mg, 95%) as a viscous liquid. [α]2D6 = +13.8 (c = 1.0, CHCl3).
1
IR (neat): ν = 3472, 2928 cm–1. H NMR (400 MHz, CDCl ): δ =
˜
3
1.00 (s, 9 H), 1.24 (s, 3 H), 1.28 (s, 3 H), 2.97 (s, 3 H), 3.46–3.47
(m, 2 H), 3.66 (dd, J = 12.5, 6.0 Hz, 1 H), 3.74–3.76 (m, 1 H), 3.87
(dd, J = 9.2, 4.6 Hz, 1 H), 4.17 (m, 1 H), 4.28 (m, 1 H), 4.66 (dt,
liquid. [α]2D6 = +27.3 (c = 1, CHCl ). IR (neat): ν = 3414, 2982,
˜
3
1265, 1225, 1079, 808 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.40 J = 5.8, 3.6 Hz, 1 H), 7.29–7.35 (m, 6 H), 7.60–7.67 (m, 4 H) ppm.
(s, 3 H), 1.43 (s, 3 H), 3.05 (s, 3 H), 3.57 (dd, J = 6.4, 9.7 Hz, 1 H),
3.74 (dd, J = 3.0, 9.7 Hz, 1 H), 3.79–3.88 (m, 3 H), 4.07–4.10 (m,
1 H), 4.35 (dd, J = 4.2, 6.6 Hz, 1 H), 4.57 (AB quartet, J = 11.6 Hz,
13C NMR (100 MHz, CDCl3): δ = 19.2, 26.9, 27.1, 27.2, 38.5, 61.4,
62.9, 72.9, 75.8, 79.1, 81.9, 110.0, 127.7, 127.7, 129.9, 129.9, 133.5,
135.6, 135.8 ppm. HRMS(ESI): calcd. for C26H38O8SSiNa [M +
2 H), 4.59 (s, 2 H), 5.05–5.08 (m, 1 H), 7.33–7.38 (m, 10 H) ppm. Na]+ 561.1954; found 561.1970.
13C NMR (100 MHz, CDCl3): δ = 26.8, 26.9, 38.4, 68.6, 71.2, 71.7,
(R)-1-[(4R,5R)-2,2-Dimethyl-5-(oxiran-2-yl)-1,3-dioxolan-4-yl]eth-
73.2, 78.6, 80.8, 110.1, 127.5, 127.6, 127.7, 128.2, 128.3, 137.1,
137.7 ppm. HRMS (ESI): calcd. for C24H32O8SNa [M + Na]+
503.1720; found 503.1716.
ane-1,2-diol (9): To a stirred solution of compound 8 (220 mg,
0.40 mmol) in dry THF (5 mL) was added TBAF (1 m solution in
THF, 1.6 mL). The reaction mixture was stirred at room tempera-
ture for 6 h and then was concentrated. Purification over silica gel
by column chromatography (gradient elution with 50–60% EtOAc
in hexane) yielded pure compound 9 (70 mg, 84%) as a colorless
(R)-1-{(4S,5R)-5-[(R)-1,2-Dihydroxyethyl]-2,2-dimethyl-1,3-dioxo-
lan-4-yl}-2-hydroxyethyl Methanesulfonate (6): To a stirred solution
of compound 5 (120 mg, 0.25 mmol) in methanol (10 mL) was
added Pd/C (10 wt.-%, 12 mg). The reaction mixture was stirred
under a hydrogen atmosphere (60 psi) for 3 d. The reaction was
filtered and then concentrated under reduced pressure to yield the
crude compound. Purification of the crude compound over silica
gel by column chromatography (gradient elution with 80–100%
EtOAc in hexane) gave pure compound 6 (70 mg, 93%) as a color-
liquid. [α]2D6 = +0.8 (c = 1, CHCl ). IR (neat): ν = 3412, 2988, 1372,
˜
3
1255, 1215, 1064, 858 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.40
(s, 6 H), 2.81–2.85 (m, 2 H), 3.15 (dd, J = 3.6, 7.0 Hz, 1 H), 3.70–
3.78 (m, 2 H), 3.83 (dd, J = 2.8, 10.4 Hz, 1 H), 3.96–4.01 (m, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.5, 27.0, 44.9, 52.0,
63.7, 72.5, 77.8, 78.7, 109.9 ppm. HRMS (ESI): calcd. for
C9H16O5Na [M + Na]+ 227.0895; found 227.0900.
less liquid. [α]2D6 = –10.6 (c = 1, CHCl ). IR (neat): ν = 3412, 2988,
˜
3
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Eur. J. Org. Chem. 2011, 6980–6988